This study explores the enhancement of α-Fe2O3 (hematite) nanorod arrays for photoelec-trochemical applications by constructing a Cu2ZnSnS4 (CZTS) heterojunction. While α-Fe2O3 offers good stability, a low cost, and environmental benefits, its efficiency is limited by slow oxygen evolution kinetics, high carrier recombination rates, and low conductivity. By introducing CZTS, a material with strong light absorption and charge transport properties, we enhance the separation of photogenerated charge carriers, reduce charge transfer resistance, and increase the carrier concentration, thereby boosting the overall photoelectrochemical performance. The experimental results show that a modified FC-15 photoanode achieves a photocurrent density of 3.40 mA/cm2 at 1.60 V vs. RHE, a substantial increase compared to 0.40 mA/cm2 for unmodified α-Fe2O3. Band gap analysis reveals a reduced band gap in the FC-15 material, enhancing light absorption and boosting the photoelectrocatalytic performance. In photoelectrochemical water-splitting tests, the FC-15 photoanode achieves a hydrogen production rate of 41.6 μmol/cm2/h, which is significantly improved over the unmodified sample at 5.64 μmol/cm2/h. These findings indicate that the CZTS/α-Fe2O3 heterojunction effectively promotes charge separation, enhances charge transport, and improves light absorption, substantially increasing photocatalytic efficiency. This heterojunction approach offers new insights and technical strategies for developing photocatalytic materials with potential applications in renewable energy.